title: Precursor transformation during molecular oxidation catalysis with organometallic iridium complexes.
abstract: We present evidence for Cp* being a sacrificial placeholder ligand in the [Cp*Ir(III)(chelate)X] series of homogeneous oxidation catalysts. UV-vis and (1)H NMR profiles as well as MALDI-MS data show a rapid and irreversible loss of the Cp* ligand under reaction conditions, which likely proceeds through an intramolecular inner-sphere oxidation pathway reminiscent of the reductive in situ elimination of diolefin placeholder ligands in hydrogenation catalysis by [(diene)M(I)(L,L')](+) (M = Rh and Ir) precursors. When oxidatively stable chelate ligands are bound to the iridium in addition to the Cp*, the oxidized precursors yield homogeneous solutions with a characteristic blue color that remain active in both water- and CH-oxidation catalysis without further induction period. Electrophoresis suggests the presence of well-defined Ir-cations, and TEM-EDX, XPS, (17)O NMR, and resonance-Raman spectroscopy data are most consistent with the molecular identity of the blue species to be a bis-μ-oxo di-iridium(IV) coordination compound with two waters and one chelate ligand bound to each metal. DFT calculations give insight into the electronic structure of this catalyst resting state, and time-dependent simulations agree with the assignments of the experimental spectroscopic data. [(cod)Ir(I)(chelate)] precursors bearing the same chelate ligands are shown to be equally effective precatalysts for both water- and CH-oxidations using NaIO4 as chemical oxidant.
authors.affiliation: Department of Chemistry, Yale University, New Haven, Connecticut 06520, USA
authors.forename: Ulrich
authors.initials: U
authors.lastname: Hintermair
authors.forename: Stafford W
authors.initials: SW
authors.lastname: Sheehan
authors.forename: Alexander R
authors.initials: AR
authors.lastname: Parent
authors.forename: Daniel H
authors.initials: DH
authors.lastname: Ess
authors.forename: David T
authors.initials: DT
authors.lastname: Richens
authors.forename: Patrick H
authors.initials: PH
authors.lastname: Vaccaro
authors.forename: Gary W
authors.initials: GW
authors.lastname: Brudvig
authors.forename: Robert H
authors.initials: RH
authors.lastname: Crabtree